Azo dyestuff insoluble in water and fiber dyed therewith



.zene, naphthalene or anthracene series which z i formula within the brackets) arenamed for the Patented Aug. 21, 1934 i' 1 UN I STAT PATENT 1 o-FFlcs AZO'DYESTUFF IN SOLUBLE IN WATER AND FIBER DYE!) THEREWITH Leopold Laska and Arthur Zitscher, Offenbachvon-the-lvlain', Germany, .assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application August '7, 1931, Serial No. 555,860. In Germany August'15, 1930 12 Claims. (01.260-97) Our present invention relates to azodyestuffs insoluble in water and to fiber dyed therewith.

These dyestuffs correspond probably to the general formula:

wherein the nuclei 1' and Ill may be substituted by alkyl, alkoxy or halogen, n means the number 1 or 2 and R an aromatic radical of the benmay be substituted by alkyl,' alkoxy, aryloxy, halogen or nitro groups.

Throughout this specification the combining components'of ourrdyestufis (shown in the above sake of convenience V (3 hydroxy-diphenylamine-- 4 c carbonyl) amino -benzen'es The dyestufis may beproduced in substance and used for making color lakes or they may be pre pared on fibers. As fibers suitable for the production ofthese dyestuffs'thereon may be named:

cotton; wool, native and regenerated cellulose (viscose), ethers and esters of cellulose (acetate silk) .5 e When these dyestuifs are prepared on the fiber ,1 according to the ice-color method an intermediate 'drying operation may be dispensed *with on account of the afiini'ty of the arylamidesto the fibers. Thereby mainly brown dyeings are produced, ranging to brownish black and black according to the'diazo compound used, especially suitable for the batic style of dyeing,

The (3-hydroxy-diphenyl-amine 5-carbonyl amin0-benzenes used as combining components in the production of our new dyestufis may be prepared according to U. S.-.Patent No. 1;893,Q91

- by condensing 3.5-dihydroxy benzoic acid with Z-mqlecular proportions of an varylamine or by condensing a 1-arylamino-3-hydroxy-5-benzoic acid (described in the aforesaid U. S. Patent) with an aryl amine.

Inorder toiurther illustrate our invention; the

followingexamples-are given, We wish it, how ever; to be understood that we are not limited to the particular products or reaction conditions mentioned therein. p

Example 1 Well boiled and dried cotton yarn is impregnated with a solution containing per liter 1-0 grs. of 1-(4'-ch1oro-3-hydroxy-diphenylamine- '5-carbony1)aminol-chloro-benzene, 20 cc. of

caustic soda lye 01 34 B., 20 .cc; of Turkey red oil and 15 grs. of common salt. The goods are Well wrung out and developed with a solution containing per liter the diazo compound of 1.62 grs. of 2.5-dichlcro-1-amino-benzene and being neutralized with sodium bicarbonate. Then they ar rinsed and soaped at the boil; i r I In this manner a reddish browndyeingis obtained. The dyestuff thus produced on the fiber corresponds probably to the formula; t 1

By developing the impregnated goodswith diazotized:

4-ch-loro-2-nitro-1- amino v c I a a benzene a reddish brown 5-chloro- 2-'methyl-1 -'ami- Y i i no-benzene a yellowish brown 4-nitro-2-methoxy-lamine benzene a dark reddish brown 1 4 amino ahthraquihoneajreddish dyel ing is produced;

Example 2 "2.4.5 trichloro-l-aminof jphenyl ether ing is obtained. The dyestufi thus produced on the fiber corresponds probably to the formula:

3 chloro- I- amino-ben- Shades zene an orange brown 2.5 dichloro 1 amino benzene a reddish brown benzene a reddish brown chloro 2 phenoxy -1- amino-benzene a reddish brown 4 nitro 2 methoxy 1 amino-benzene a dark reddish brown 1 aminoanthraquinone a reddish brown 1-(3-hydroxy Q diphenylamine 5 carbonyl) amino-4-methyl-benzene yields on cotton with the diazo compound of:

Shades 2.5 dichloro amino-benzeneareddish brown 2.5 dichloro 4 methyl 1'- amino-benzene a brownish red 4 chloro-2-nitro-1-amino ben zen'e anorangebrown 1 (3-hydroxy 4' chloro-diphenylamine-5- carbonyl) amino-2-methyl-benzene yields on cotton with the diazo compoud of:

V Shades 2.5-dich1oro-1-amino-benzene an orange brown 1-(3-hydroxy-4-chloro-diphenylamine 5 carbonyl) amino-4-chloro-benzei1e yields on viscose with the diazo compound of:

2.5 dichloro 1 amino Shades .benzene abrownish orange 2 amino 4 chloro diacopper 1 (3 hydroxy 4' methyl diphenylamine 5-carbonyl)aminoi-methyl-benzene yields on wool with the diazo compound of:

5 chloro 2 methyl 1 Shades amino benzene a brownish red 3 chloro 1 amino-ben- 'zene I i a brownish red 5 chloro- 2 1 methoxy-lamino benzene a brownish claret red Shades 2.5 dichloro 1 amino-benzene a brown 2 amino 4 chloro diphenylether a brown The structural formulae given for our new azo dyestufis are correct to the best of our knowledge and belief. However, it has not yet been possible to definitely determine the exact structure of these new azo dyestuffs. For example, it is conceivablethatthe azo group may be attached to the phenyl nucleus II in one of the ortho-positions tothe hydroxyl group instead of in paraposition, as indicated in the structural formulae given. Consequently we wish it understood that when such structural formulae are employed in the appended claims, they are intended to define the new azo dyestuffs which we have described and which may be obtained in acordance with our disclosure.

We claim:

1. The azo dyestuffs corresponding to the genfoo eral formula:

wherein X means alkyl, alkoxy or halogen, the nucleus III may be substituted by alkyl, alkorzy or halogen and R means an aromatic radical of the benzene, naphthalene or anthracene series which may be substituted by alkyl, alkoxy, aryloxy, halogen or nitro groups, which compounds are insoluble in water and yield when pro'duced on fibers brownish dyeings. I

3. The azo dyestuffs corresponding-to the gen- 13 5 eral formula:

' R-iN: GO-NH-O-Ci wherein R means an aromatic radical of the benzene, naphthalene or anthracene series which may be substituted by alkyl, alkoxy, aryloxy, halogen or nitro groups, which compounds are insoluble in water and yield when produced on fibers brownish dyeings. 15o

4. The azo dyestuff corresponding to the formula:

which compound is insoluble inwater and yields when produced on fibers reddish brown dyeings.

5'. The azo dyestuff corresponding to the formula:

which compound is insoluble in water and yields when produced on fibers dark reddish brown dyeings.

6. The azo dyestutf corresponding to the formula: 

